Luminescent groups in very weakly degraded polystyrene

Unstabilized polystyrene samples from various producers, as well as carefully purified laboratory polymers, have been investigated by u.v.-absorption, fluorescence, phosphorescence and i.r. spectroscopy. The emission spectra of all samples indicate fluorescent and phosphorescent chromophores. In u.v.-absorption, the chromophores give rise to a long wavelength tail below the absorption edge of the phenyl groups. The phosphorescence spectrum is due to acetophenone-type end-groups of degraded polymer chains. Ultra-violet-fluorescence is due to monomeric styrene and trans-stilbene groups which probably can be formed at head-to-head sites of the polymer. Fluorescence in the blue spectral region may be due to chromophores formed by conjugated double bonds and phenyl groups. The chromophores are present in all commercial samples investigated and, at smaller concentrations, in the laboratory products also.